Pressure-sensitive adhesive sheet for application to skin

ABSTRACT

The problem of the present invention is to provide a pressure-sensitive adhesive sheet for skin adhesion, having an adhesive layer, which can be formed without using an organic solvent, shows superior adhesion performance to the skin, and shows extremely mild irritation to the skin and stratum corneum damage. To solve the problem, the present invention provides a pressure-sensitive adhesive sheet for skin adhesion, which has a substrate and an adhesive layer laminated on the substrate, wherein the adhesive layer is obtained by curing an adhesive composition containing polyether polymer (A) having at least one alkenyl group on the terminal, compound (B) having 1-10 hydrosilyl groups in a molecule and hydrosilylation catalyst (C).

TECHNICAL FIELD

This application is a U.S. National Stage of International ApplicationNo. PCT/JP2004/014683, filed Sep. 29, 2004.

The present invention relates to a pressure-sensitive adhesive sheet forskin adhesion, which is used in the medical field.

BACKGROUND ART

Various forms of pressure-sensitive adhesive sheets are used in themedical field, such as surgical tape, adhesive bandage, film dressingmaterials for wound treatment, a base material for fixing electrode forelectrocardiographic measurement and the like. Many of the adhesivesused for conventional medical pressure-sensitive adhesive sheets aremade of acrylic polymers. Acrylic polymer is generally applied, forexample, to a supportive substrate and release paper after adjustingviscosity with an organic solvent and the like. The organic solvent usedfor adjusting the viscosity is removed by volatilization afterapplication. In so doing, the organic solvent is sometimes not removedsufficiently (insufficient drying), and the organic solvent may remainin the adhesive. When a pressure-sensitive adhesive sheet having aconstitution where an adhesive directly touches the human body, such asan adhesive bandage and the like, is not dried sufficiently, the organicsolvent remaining in the adhesive, which is absorbed into the body fromthe skin, may cause inflammation such as exanthema and the like. Inaddition, the organic solvent removed in the drying step is feared tocause environmental pollution and endanger the health and safety of theworkers.

As a production method of conventional solvent-free pressure-sensitiveadhesive tapes, a hotmelt method comprising heating, kneading and/ormelting an adhesive for hotmelt and applying the same to a substrate, anemulsion method comprising applying an emulsion adhesive to a substrateand drying the same, an extrusion polymerization method comprisingextruding a thermally polymerizable monomer liquid on a substrate whileheating, kneading and polymerizing in a heating barrel, aphotopolymerization method comprising applying a photopolymerizablemonomer liquid to a substrate and exposing the same to light irradiationin an inert atmosphere to allow polymerization and the like are known.They are unsatisfactory from the viewpoints of workability (introductioninto apparatus for light irradiation, reaction time), cost and the like,and from the viewpoints of adhesion performance such as adhesion to theskin, irritation, glue remainder and the like, and no production methodcan be preferably used for medical pressure-sensitive adhesive sheetssuch as adhesive bandage and the like.

As one embodiment of solvent-free adhesives, adhesives using urethanecrosslinking, which use an oxyalkylene polymer, are known(JP-A-7-310066, JP-A-2002-60456). The aforementioned adhesives have beenreported to be superior in adhesion to the skin, moisture permeability,water absorbability and the like. However, the adhesive is associatedwith problems in that the curing speed is difficult to control becauseof urethane crosslinking, and unreacted isocyanate has toxicity.

DISCLOSURE OF THE INVENTION

It is therefore an object of the present invention to provide apressure-sensitive adhesive sheet for skin adhesion, that can be formedwithout using an organic solvent, can be easily adhered to the skin,does not irritate the skin easily, and that does not damage stratumcorneum easily.

The present inventors have conducted intensive studies in an attempt tosolve the aforementioned problems and completed the present inventionhaving the following characteristics.

[1] A pressure-sensitive adhesive sheet for skin adhesion, whichcomprises a substrate and an adhesive layer laminated on theaforementioned substrate, wherein

the adhesive layer is obtained by curing an adhesive compositioncomprising polyether polymer (A) having at least one alkenyl group onthe terminal, compound (B) having 1-10 hydrosilyl groups in a moleculeand hydrosilylation catalyst (C).

[2] The pressure-sensitive adhesive sheet of [1], wherein the polymer(A) is a polyether polymer having an alkenyl group represented by thefollowing formula (1) or (2),H₂C═C(R¹)—  (1)HC(R¹)═CH—  (2)wherein R¹ is a hydrogen atom or a hydrocarbon group having 1 to 10carbon atoms, and

the catalyst (C) is a platinum complex that does not contain a conjugatebase of a strong acid as a ligand.

[3] The pressure-sensitive adhesive sheet of [2], wherein R¹ is ahydrogen atom or a methyl group.

[4] The pressure-sensitive adhesive sheet of [2] or [3], wherein theabove-mentioned platinum complex is a platinum-vinyl siloxane complex.

[5] The pressure-sensitive adhesive sheet of [4], wherein theplatinum-vinyl siloxane complex is aplatinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex or aplatinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanecomplex.

[6] The pressure-sensitive adhesive sheet of any of [1] to [5], whereinthe main chain of the polymer (A) has a polyoxypropylene skeleton.

[7] The pressure-sensitive adhesive sheet of any of [1] to [6], whereinthe polymer (A) has a number average molecular weight in polystyreneconversion of 3000-50000 as measured by size-exclusion chromatography.

[8] The pressure-sensitive adhesive sheet of any of [1] to [7], whereinthe proportion of the toluene-insoluble component in the adhesive layeris 10-50 wt %.

[9] The pressure-sensitive adhesive sheet of any of [1] to [8], whichhas a moisture permeability of not less than 800 g/m²·24 hr, as measuredunder the conditions of thickness of adhesive layer 50 μm, temperature40° C. and relative humidity 30%.

DETAILED DESCRIPTION OF THE INVENTION

The pressure-sensitive adhesive sheet of the present invention has asubstrate and an adhesive layer. Of these, the adhesive layer isobtained by curing an adhesive composition comprising theabove-mentioned polymer (A), compound (B) and catalyst (C).

Polymer (A) is a polyether polymer having at least one alkenyl group onthe terminal. The alkenyl group is not particularly limited as long asit contains a carbon-carbon double bond active for a hydrosilylationreaction. As the alkenyl group, an aliphatic unsaturated hydrocarbongroup preferably having 2-20, more preferably 2-4, carbon atoms (e.g.,vinyl group, allyl group, methylvinyl group, propenyl group, butenylgroup, pentenyl group, hexenyl group etc.), a cyclic unsaturatedhydrocarbon group preferably having 3-20, more preferably 3-6, carbonatoms (e.g., cyclopropenyl group, cyclobutenyl group, cyclopentenylgroup, cyclohexenyl group etc.), methacrylic group and the like can bementioned.

Since synthesis reaction can be easily carried out, a preferable alkenylgroup is a group represented by the following formulas (1) and (2). Inthe following formulas, R¹ is a hydrogen atom or a hydrocarbon grouphaving 1 to 10 carbon atoms, with preference given to a hydrogen atomand a methyl group.H₂C═C(R¹)—  (1)HC(R¹)═CH—  (2)

The polymer (A) has at least one, preferably 1-5, more preferably 1-3,still more preferably 1-2, alkenyl groups in one molecule (polymer) onaverage. When the number of alkenyl groups in 1 molecule of polymer (A)is less than one on average, curing becomes difficult, and when thenumber of alkenyl groups contained in 1 molecule is too high, thenetwork structure becomes dense and the adhesive property tends to bedegraded.

As a typical example of polyether polymer, which is the basic skeletonof polymer (A), a polyoxyalkylene polymer comprising a repeating unitrepresented by the formula (—R²—O—) can be mentioned, wherein R² is adivalent alkylene group. In view of easy availability and easy handling,the main chain of preferable polymer (A) has a polyoxypropyleneskeleton. In other words, the above-mentioned R² is preferably—CH₂CH(CH₃)—. The polyether polymer may be made of one kind of repeatingunit or multiple repeating units. The polyether polymer may be a linearpolymer or branched polymer.

While the whole polymer (A) other than the alkenyl group is preferablymade of a polyether skeleton, other structure unit may also becontained. In this case, the total proportion of the polyether skeletonin polymer (A) is preferably not less than 80 wt %, more preferably notless than 90 wt %.

In view of easy operation at room temperature, and superior adhesiveproperty, the number average molecular weight of polymer (A) ispreferably 3000-50000, more preferably 6000-50000, and particularlypreferably 10000-30000. When the number average molecular weight is lessthan 3000, the obtained cured product tends to become brittle, and whenthe number average molecular weight exceeds 50000, the adhesivecomposition becomes highly viscous and difficult to handle. Theabove-mentioned number average molecular weight is a number averagemolecular weight based on polystyrene, as measured by size-exclusionchromatography.

The binding mode of the alkenyl group to a polyether polymer is notparticularly limited. As the bond between the alkenyl group and thepolyether polymer, a direct bond, an ether bond, an ester bond, acarbonate bond, a urethane bond, a urea bond and the like can bementioned.

The production method of polymer (A) is not particularly limited and,for example, a method comprising producing a polyether polymer and thenintroducing an alkenyl group thereinto can be mentioned. In this case,various known production methods can be adopted for the polyetherpolymer, or, commercially available polyether polymer may be used. Themethod for introducing an alkenyl group into a polyether polymer is alsoknown and, for example, a method of copolymerizing a monomer having analkenyl group (e.g., allylglycidylether) and a monomer for synthesizinga polyether polymer, a method comprising reacting a polyether polymerwherein a functional group (e.g., hydroxyl group, alkoxide group) hasbeen introduced in advance into a desired part (main chain terminaletc.) with a compound having both a functional group reactive with thefunctional group and an alkenyl group (e.g., acrylic acid, methacrylicacid, vinyl acetate, acrylic acid chloride etc.) and the like can bementioned.

The compound (B) has 1-10 hydrosilyl groups in a molecule. Thehydrosilyl group means a group having a Si—H bond. In the presentinvention, when two hydrogen atoms (H) are bonded to one silicon atom(Si), two hydrosilyl groups are considered to be present. The chemicalstructure of compound (B) other than the hydrosilyl group is notparticularly limited. The number average molecular weight of compound(B) as calculated from the SiH group value measured from the amount ofgenerated hydrogen is preferably 400-3000, more preferably 500-1000.When the number average molecular weight is too low, volatilizationeasily occur during heat-curing, and cured product is difficult toobtain, and when it is too high, the curing rate tends to be low.

The number of hydrosilyl groups contained in one molecule of compound(B) is 1-10, preferably 2-8. When compound (B) has not less than 2hydrosilyl groups, multiple polymers (A) can be crosslinked during cureand the resulting pressure-sensitive adhesive sheet expresses apreferable cohesion force. As a result, glue remainder and the like donot occur easily when the pressure-sensitive adhesive sheet is adheredto the skin and peeled off thereafter. However, when the number ofhydrosilyl groups is too many, the crosslinking becomes too dense, andthe obtained pressure-sensitive adhesive sheet tends to show degradedadhesive property such as adhesion to the skin, tacky feeling and thelike. Furthermore, the stability of compound (B) becomes poor, a largeamount of hydrosilyl group remains after curing in the cured product topossibly cause irritation to the skin and voids. The level of density ofcrosslinking greatly affects the level of density of the main chainpolyether parts of polymer (A), which in turn affects the moisturepermeability of the pressure-sensitive adhesive sheet as a whole. Thus,the number of hydrosilyl groups of compound (B) should be determined inconsideration of the balance between the moisture permeability and theadhesive property. Compound (B) may be used alone or in combination oftwo or more kinds thereof. It is preferable that compound (B) be highlycompatible with polymer (A).

In view of easy availability of starting materials and compatibilitywith polymer (A), preferable compound (B) is organohydrogen siloxanemodified with an organic group. A typical example of organohydrogensiloxane is a compound represented by the following formula (3):

The value of a in the formula (3) corresponds to the number ofhydrosilyl group in one molecule. While the value of a+b is notparticularly limited, it is preferably 2-50, more preferably 2-20. Inthe formula, R is a hydrocarbon group having 2-20 (preferably 4-12)carbon atoms in the main chain, which is specifically a monovalentresidue obtained by cleaving the double bond of the below-mentionedorganic compound (allyl compound). The compound of the formula (3) canbe obtained by modifying unmodified methylhydrogensilicone to introducea hydrocarbon group R. The unmodified methylhydrogensilicone correspondsto a compound of the formula (3) wherein each R is H, and is used as astarting material for various modified silicones, as described in“Market Prospect for Silicone—Manufacturer Strategy, Application andDevelopment—”, CMC Publishing CO., LTD. (1990.1.31). As the organiccompound (allyl compound) used for introduction of R, α-olefin, styrene,α-methylstyrene, allyl alkyl ether, allyl alkyl ester, allyl phenylether, allyl phenyl ester and the like can be mentioned. The number ofhydrosilyl groups that the modified molecule has can be controlled bythe amount of the aforementioned organic compound to be added formodification (see Examples).

The amount ratio of polymer (A) and compound (B) in the adhesivecomposition used for forming an adhesive layer is expressed by the ratioof the total amount of the hydrosilyl group derived from compound (B) tothe total amount of the alkenyl group derived from polymer (A). Thelevel of crosslinking density after curing is determined by the totalamount of hydrosilyl group per 1 mol of the total amount of the alkenylgroup in the adhesive composition. In consideration of the balancebetween appropriate adhesiveness and small glue remainder and the like,the total amount of hydrosilyl group per 1 mol of the total amount ofalkenyl group is preferably 0.3-0.8 mol, more preferably 0.4-0.7 mol.

The catalyst (C), i.e., hydrosilylation catalyst, is not particularlylimited, and any can be used as long as it promotes the hydrosilylationreaction. Specifically, chloroplatinic acid, platinum-vinylsiloxanecomplexes (e.g., platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxanecomplex,platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanecomplex), platinum-olefin complexes (e.g., Pt_(x) (ViMe₂SiOSiMe₂Vi)_(y),Pt[(MeViSiO)₄]_(z) (wherein x, y and z are each a positive integer)) andthe like can be mentioned. Of these, from the aspect of catalystactivity, a platinum complex catalyst free of a conjugate base of astrong acid as a ligand is preferable, platinum-vinylsiloxane complex ismore preferable, and platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxanecomplex andplatinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanecomplex are particularly preferable.

The amount of catalyst (C) is not particularly limited, and it ispreferably 10⁻⁸-10⁻¹ mol, more preferably 10⁻⁶-10⁻³ mol, per 1 mol ofalkenyl group of polymer (A) in the adhesive composition. When theamount is within the above-mentioned range, appropriate curing rate,stable curability, ensured pot life as requested and the like can beeasily achieved.

The adhesive composition may contain components other than theabove-mentioned (A)-(C). As such component, tackifier, adhesiveadditive, storage stabilizer for compound (B), and other components canbe mentioned.

As the tackifier and adhesive additive, phenolic resin, modifiedphenolic resin, terpene phenol resin, xylene phenol resin,cyclopentadiene-phenol resin, xylene resin, petroleum resin,phenol-modified petroleum resin, rosin ester resin, low molecular weightpolystyrene resin, terpene resin and the like can be mentioned. Whenthese are used to improve adhesive property, they may be used alone orin combination of two or more kinds thereof. The amount of thesetackifiers and adhesive additives is preferably 10-100 parts by weight,more preferably 15-50 parts by weight, per 100 parts by weight of thetotal amount of polymer (A) and compound (B). When the amount used istoo high, the adhesive layer unpreferably shows degraded moisturepermeability.

As the storage stabilizer for compound (B), aliphatic compound having anunsaturated bond, organic phosphorus compound, organic sulfur compound,nitrogen-containing compound, tin compound, organic peroxide and thelike can be mentioned, which provide an effect of improving the pot lifeof an adhesive composition.

The adhesive composition used for forming an adhesive layer may containa water-soluble organic polymer or a water absorbable polymer forimproving water resistance, sweat resistance, water absorbability andthe like of the adhesive layer. Moreover, other plasticizer, softeningagent, filler, pigment, surfactant, UV absorber, antioxidant,antibacterial agent and the like may be further added. While the use ofan organic solvent here is not preferable, the use thereof is notentirely denied.

The adhesive layer of the pressure-sensitive adhesive sheet of thepresent invention can be obtained by curing the aforementioned adhesivecomposition. The curing here means a hydrosilylation reaction betweenpolymer (A) and compound (B) by heating. The cure conditions include,for example, standing at 40-180° C. for 1-60 min. To make curing morecomplete, the adhesive composition may be left standing at 40-80° C. forseveral days. The level of curing can be expressed by the proportion (wt%) of the toluene-insoluble component in the adhesive layer. Thetoluene-insoluble component refers to a component insoluble even afterimmersion in toluene for 7 days. The specific test steps to determinethe above-mentioned proportion is described in the following Examples.Preferably, the proportion of the toluene-insoluble component in theadhesive layer is 10-50 wt %. When the proportion is within this range,cohesive failure does not occur easily whether or not the adhesivecomposition is completely cured. The cohesive failure here meansadhesive remainder on the skin when the obtained pressure-sensitiveadhesive sheet is adhered to the skin and then peeled off. The amount ofthe toluene-insoluble component can be controlled by the amount ratio ofthe aforementioned polymer (A) and compound (B) (ratio of the totalamount of alkenyl group and the total amount of hydrosilyl group) andcure conditions.

The viscosity during curing is preferably 10-1000 Pa·s. The viscositycan be controlled by the amount ratio of components (A)-(C) and the kindand amount of the aforementioned storage stabilizer for compound (B). Toincrease the viscosity, for example, the following means can bementioned.

To lower the temperature of the adhesive composition to be applied.

To allow pre-gelation of polymer (A) by adding a small amount ofcompound (B).

The substrate to be used for the pressure-sensitive adhesive sheet ofthe present invention is not particularly limited as long as it can holdan adhesive composition before curing. The materials of the substrateinclude urethane polymers such as polyetherurethane and the like, amidepolymers such as polyetheramide and the like, acrylic polymers such aspolyacrylate and the like, olefin polymers such as polyethylene,polypropylene, ethylene-vinyl acetate copolymer and the like, esterpolymers such as polyether polyester and the like, and the like. Thesubstrate may be a single layer or a laminate comprising multiplelayers. In the case of a laminate, the layers may be made of the samematerial or different kinds of materials. It is preferable to select thematerial of a substrate from fabric such as non-woven fabric, wovenfabric and the like, and vapor permeable polymer sheet, to preventgetting sweaty and the like during application to the skin. For the samereasons, the substrate may be appropriately perforated. The thickness ofthe substrate is not particularly limited, and can be appropriatelydetermined according to the object and use. It is, for example, 10-5000μm. The pressure-sensitive adhesive sheet of the present inventionwidely encompasses the sheets having an about plate shape, and includesnot only the “sheet” but also those that can be referred to as a “film”.

A method of forming an adhesive layer on a substrate is not particularlylimited and, for example, a method comprising applying an adhesivecomposition to one surface of the substrate and curing same under theaforementioned conditions, and a method comprising applying a releasingagent to a sheet (release sheet) in advance, applying an adhesivecomposition, curing and adhering the sheet to a substrate can bementioned. As the releasing agent, various silicone, olefin or fluorinereleasing agents and the like are known, which can be usedappropriately. Of these, olefin releasing agents and non-solventaddition curing type silicone releasing agents are preferable from theaspects of cost and ensured release property.

The thickness of the adhesive layer is not particularly limited, and itis, for example, 10-5000 μm.

The pressure-sensitive adhesive sheet for skin adhesion of the presentinvention preferably shows a tensile stress of 0.3-3.0 N/20 mm, morepreferably 0.6-1.5 N/20 mm, after adhesion to the skin (back) of humanbody, and peeling off 6 hr later at a peeling rate of 300 mm/min and ata peeling angle of 180 degrees. In addition, the area ratio of detachedstratum corneum upon peeling off is preferably not more than 30%, morepreferably 0-10%. When the tensile stress caused by peeling off from theskin is within the above range, the adhesive sheet has sufficient skinadhesive force, and can be peeled off without damaging the skin. Inaddition, it shows a sufficient adhesive force even after repeatedadhesion. To improve the above-mentioned tensile stress, the molecularweight between crosslinks of the adhesive may be increased, thecrosslinking density may be decreased, the moisture permeability of thepressure-sensitive adhesive sheet as a whole may be raised and the like.The above-mentioned tensile stress can be decreased by performingconversely. To decrease the above-mentioned area ratio of detachedstratum corneum, the moisture permeability of the pressure-sensitiveadhesive sheet as a whole may be increased, the crosslinking density maybe increased, and the like.

The pressure-sensitive adhesive sheet for skin adhesion of the presentinvention has a moisture permeability of not less than 800 g/m²·24 hr,more preferably 800-3000 g/m²·24 hr, as measured under the conditions ofthickness of adhesive layer 50 μm, temperature 40° C. and relativehumidity 30%. When the moisture permeability of the pressure-sensitiveadhesive sheet as a whole is within this range, sweatiness andirritation to the skin from adhesion for a long time can be prevented.The specific measurement method of the moisture permeability ismentioned below. While the moisture permeability of thepressure-sensitive adhesive sheet naturally depends on the material andstructure of the substrate and the like, the use of the aforementionedadhesive composition expands the range of choices for the substrate thataffords the above-mentioned preferable moisture permeability. To improvethe moisture permeability of the pressure-sensitive adhesive sheet,crosslinking density of the adhesive may be increased, the proportion ofpolyether unit in polymer (A) may be increased and the like.

The pressure-sensitive adhesive sheet “for skin adhesion” refers tosheet in general, which is adhered to the skin for the prophylaxis ortreatment of illness or wounds, diagnosis of health condition, fixing acatheter and the like to the skin surface and the like. Thepressure-sensitive adhesive sheet may or may not further contain amedicinal ingredient. Specific examples of the pressure-sensitiveadhesive sheet for skin adhesion include, but are not limited to,surgical tape, adhesive bandage, film dressing materials for woundtreatment, a base material for fixing electrode for electrocardiographicmeasurement and the like.

EXAMPLES

The present invention is explained in detail in the following byreferring to Examples, which are not to be construed as limitative.Various modifications and changes may be made to the present inventionwithout departing from the technical scope of the invention.

(Synthesis of Polymer A-1)

By polymerization using a mixed metal cyanide complex (zinc hexacyanocobaltate) and caustic alkall as a catalyst, polyoxypropylene glycolhaving a number average molecular weight of 3000 was obtained. Using thepolyoxypropylene glycol as an initiator, propylene oxide was polymerizedto give an oxypropylene polymer. The oxypropylene polymer was applied tothe method of Synthetic Example 1 of JP-A-5-117521 to give a polymerhaving a number average molecular weight of 28000. The terminal of thepolymer was converted to an allyl group using a 28% methanol solution ofsodium methylate and allyl chloride, and the polymer was purified bydesalting to give a polyoxyalkylene polymer (polymer A-1) generallyhaving two terminal allyl groups in one molecule. The amount of theterminal allyl group of the obtained polymer was 0.12 mmol/g.

(Synthesis of Polymer A-2)

By polymerization according to the method of JP-A-5-117521, comparativeSynthetic Example 1, using caustic alkali as a catalyst,polyoxypropylene glycol having a number average molecular weight of 3000was obtained. This polyoxypropylene glycol, alkali and dihalomethanewere subjected to a molecular chain extension reaction, the terminal wasconverted to an allyl group with allyl chloride, and the polymer waspurified by desalting to give polymer A-2. The number average molecularweight of this polymer by GPC was 13800 and the polymer generally hadtwo terminal allyl groups in one molecule. The amount of the terminalallyl group relative to the weight of polymer A-2 was 0.24 mmol/g.

(Synthesis of compound B-1)

To methylhydrogensilicone represented by the following formula (4)wherein x is 5 on average was added, in the presence of a platinumcatalyst, α-methylstyrene in an amount of 0.6 equivalent relative to theamount of entire hydrosilyl group to give a compound (compound B-1)generally having two terminal allyl groups in one molecule. Thehydrosilyl group content of this compound was 2.5 mmol/g.

(Synthesis of Compound B-2)

To methylhydrogensilicone represented by the formula (4) wherein x is 5on average was added, in the presence of a platinum catalyst,α-methylstyrene in an amount of 0.4 equivalent relative to the amount ofentire hydrosilyl group to give a compound (compound B-2) generallyhaving three terminal allyl groups in one molecule. The hydrosilyl groupcontent of this compound was 4.1 mmol/g.

(Synthesis of Compound B-3)

To methylhydrogensilicone represented by the formula (4) wherein x is 10on average was added, in the presence of a platinum catalyst,α-methylstyrene in an amount of 0.5 equivalent relative to the amount ofentire hydrosilyl group to give a compound (compound B-3) generallyhaving five terminal allyl groups in one molecule. The hydrosilyl groupcontent of this compound was 4.2 mmol/g.

Examples 1-12

To a given amount of polymer A-1 or A-2 was added a given amount ofcompound B-1, B-2 or B-3 (combination and amount thereof are shown inTable 1). The mixtures were thoroughly mixed with 100 μl of aplatinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex(hydrosilylation catalyst, 3 wt %, platinum isopropanol solution) and 23mg of dimethyl maleate to give adhesive compositions. The adhesivecompositions were applied, at room temperature, to the treated surfaceof a release paper subjected to a silicone release treatment, such thatthe thickness after curing became 50 μm, and the release paper was curedat 130° C. for 3 min to give an adhesive layer. Then, a polyesternon-woven fabric (grammage 35 g/m²) was laminated on the cured adhesivelayer as a substrate under the conditions of 120° C., 5 kg/cm², rate 2m/min. In this way, pressure-sensitive adhesive sheets were prepared.

Comparative Example 1

Isononyl acrylate (65 parts), 2-methoxyethyl acrylate (30 parts) andacrylic acid (5 parts) were copolymerized and the obtained acryliccopolymer (100 parts) was dissolved in toluene (200 parts) to give ahomogeneous solution of a medical adhesive. The solution was applied tothe treated surface of a release sheet subjected to a release treatment,such that the thickness after curing became 50 μm, and the release paperwas dried at 110° C. for 3 min and transferred to a non-woven fabric(same as the above-mentioned Example) as a substrate to give apressure-sensitive adhesive sheet.

TABLE 1 SiH group/ polymer allyl group (A) compound (B) (molar tackifier(kind, g) (kind, g) ratio) resin (g) Ex. 1 A-1, 100 B-1, 2.4 0.5 0 Ex. 2A-1, 100 B-1, 2.9 0.6 0 Ex. 3 A-1, 100 B-1, 3.4 0.7 20 Ex. 4 A-1, 100B-2, 1.5 0.5 0 Ex. 5 A-1, 100 B-2, 1.8 0.6 0 Ex. 6 A-1, 100 B-2, 2.1 0.720 Ex. 7 A-1, 100 B-3, 1.4 0.5 0 Ex. 8 A-1, 100 B-3, 1.7 0.6 0 Ex. 9A-1, 100 B-3, 2.0 0.7 20 Ex. 10 A-2, 100 B-1, 4.9 0.5 40 Ex. 11 A-2, 100B-2, 3.0 0.5 40 Ex. 12 A-2, 100 B-3, 2.9 0.5 40 Com. (acrylic) Ex. 1(Proportion of Solvent (Toluene) Insoluble Component in Adhesive Layer)

An adhesive (0.5 g) was taken from each pressure-sensitive adhesivesheet, and the weight (W₁) was precisely measured. The sample wasextracted with toluene (50 g) at ambient temperature for 7 days, and theresidue (toluene-insoluble content) was filtered through apolytetrafluoroethylene porous membrane (average pore size 0.2 μm,manufactured by Nitto Denko Corporation, NTF membrane) and dried. Theweight (W₂) of the dried adhesive was precisely measured, and thesolvent (toluene)-insoluble content (wt %) was determined.Solvent-insoluble content (wt %)=(W₂×100)/(W₁)

(Skin Adhesive Force (Tensile Stress))

A pressure-sensitive adhesive sheet cut into a 20 mm width was adheredto the back of five volunteers, and press-adhered with one reciprocationof a roller weighing 1 kg. After 6 hr, the pressure-sensitive adhesivesheet was peeled off, and the release force (tensile stress) then wasmeasured. The tensile stress (N/20 mm) was measured using a tensiletester “Autograph AGS-100D” manufactured by Shimadzu Corporation underthe conditions of room temperature (23° C.), relative humidity 65%,tensile speed 300 mm/min, release angle 180°. The average value of thetensile stress of five volunteers was calculated. In addition, thedestruction of the adhesive layer after peeling off was visuallyobserved to determine whether it was cohesive failure or interfacialfracture.

(Moisture Permeability)

Distilled water (10 ml) was placed in a cylindrical glass container(inner diameter 40 mm, height 40 mm) and to the opening of the containerwas adhered and fixed a round pressure-sensitive adhesive sheet cut intoa circle (diameter 50 mm), with the adhesive layer facing down. Theweight (W₃) of the whole container with the pressure-sensitive adhesivesheet was measured, and the container was placed in a thermo-hygrostatat 40° C., relative humidity 30% and stood for 24 hr. The weight (W₄)after the lapse of 24 hr was measured and the moisture permeability wascalculated from the following formula.Moisture permeability (g/m²·24 h)=(W ₃ −W ₄)/(0.02×0.02×π)(Skin Irritation)

With the pressure-sensitive adhesive sheet after peeling off, which wasused for the measurement of the skin adhesive force, stratum corneumdetach amount was measured. Specifically, the sample sheets peeled offfrom the back of the volunteers were immersed in a stratum corneumstaining solution (Gentian Violet 1%, Brilliant Green 0.5%, distilledwater 98.5%) manufactured by Wako Pure Chemical Industries, Ltd. forabout 30 min to allow coloring of skin stratum corneum. Thereafter, thepressure-sensitive adhesive sheet was sufficiently washed with distilledwater and dried for 24 hr. The adhesive layer of the driedpressure-sensitive adhesive sheet was observed with a microscope, theimages were analyzed and the area ratio of the detached stratum corneumwas determined. The area ratio of damaged stratum corneum was an averageof five volunteers.

The measurement results of each pressure-sensitive adhesive sheet aresummarized in Table 2.

TABLE 2 skin adhesive area ratio toluene force (%) of insoluble moisture(state of damaged component permeability destruction stratum (wt %)(g/m² · 24 h) N/20 mm) corneum Ex. 1 20 1000 interface, 10 1.3 Ex. 2 25900 interface, 10 1.1 Ex. 3 30 1000 interface, 5 0.5 Ex. 4 25 900interface, 10 1.1 Ex. 5 30 1000 interface, 10 0.5 Ex. 6 35 1000interface, 10 0.5 Ex. 7 20 1500 interface, 5 0.5 Ex. 8 25 1100interface, 5 0.4 Ex. 9 30 1000 interface, 5 0.4 Ex. 10 25 1200interface, 10 0.4 Ex. 11 30 1200 interface, 10 0.4 Ex. 12 30 1800interface, 10 0.4 Com. 0 400 interface, 80 Ex. 1 1.5

INDUSTRIAL APPLICABILITY

The pressure-sensitive adhesive sheet of the present invention showssuperior adhesive property. That is, even if additives other than themain polymers, such as tackifier resin, softening agent, waterabsorbable resin and the like, are not used as adhesive components, orare used in reduced amounts, the pressure-sensitive adhesive sheet ofthe present invention shows superior adhesion performance. The substrateto be used for the pressure-sensitive adhesive sheet of the presentinvention can be freely selected depending on the use, from those havingor not having moisture permeability.

This application is based on a patent application No. 2003-347542 filedin Japan, the contents of which are hereby incorporated by reference.

1. A pressure-sensitive adhesive sheet for skin adhesion, whichcomprises a substrate and an adhesive layer laminated on the substrate,wherein the adhesive layer is obtained by curing an adhesive compositioncomprising polyether polymer (A) having a number average molecularweight of 10000-30000 and at least one alkenyl group on the terminal,compound (B) having a number average molecular weight of 500-1000 and1-10 hydrosilyl groups in a molecule and hydrosilylation catalyst (C),and the molar ratio of the hydrosilyl group/alkenyl group is 0.3-0.8. 2.The pressure-sensitive adhesive sheet of claim 1, wherein the polymer(A) is a polyether polymer having an alkenyl group represented by thefollowing formula (1) or (2),H₂C═C(R¹)—  (1)HC(R¹)═CH—  (2) wherein R¹ is a hydrogen atom or a hydrocarbon grouphaving 1 to 10 carbon atoms, and the catalyst (C) is a platinum complexthat does not contain a conjugate base of a strong acid as a ligand. 3.The pressure-sensitive adhesive sheet of claim 2, wherein R¹ is ahydrogen atom or a methyl group.
 4. The pressure-sensitive adhesivesheet of claim 2, wherein the platinum complex is a platinum-vinylsiloxane complex.
 5. The pressure-sensitive adhesive sheet of claim 4,wherein the platinum-vinyl siloxane complex is aplatinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex or aplatinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanecomplex.
 6. The pressure-sensitive adhesive sheet of claim 1, whereinthe main chain of the polymer (A) has a polyoxypropylene skeleton. 7.The pressure-sensitive adhesive sheet of claim 1, wherein the polymer(A) has a number average molecular weight in polystyrene conversion of3000-50000 as measured by size-exclusion chromatography.
 8. Thepressure-sensitive adhesive sheet of claim 1, wherein the proportion ofthe toluene-insoluble component in the adhesive layer is 10-50 wt %. 9.The pressure-sensitive adhesive sheet of claim 1, which has a moisturepermeability of not less than 800 g/m²·24 hr, as measured under theconditions of thickness of adhesive layer 50 μm, temperature 40° C. andrelative humidity 30%.
 10. The pressure-sensitive adhesive sheet ofclaim 3, wherein the platinum complex is a platinum-vinyl siloxanecomplex.
 11. The pressure-sensitive adhesive sheet of claim 10, whereinthe platinum-vinyl siloxane complex is aplatinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex or aplatinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxanecomplex.